Classifications

• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N9/00—Investigating density or specific gravity of materials; Analysing materials by determining density or specific gravity
  • G01N9/002—Investigating density or specific gravity of materials; Analysing materials by determining density or specific gravity using variation of the resonant frequency of an element vibrating in contact with the material submitted to analysis
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
  • G01N29/02—Analysing fluids
  • G01N29/036—Analysing fluids by measuring frequency or resonance of acoustic waves
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N2291/00—Indexing codes associated with group G01N29/00
  • G01N2291/02—Indexing codes associated with the analysed material
  • G01N2291/025—Change of phase or condition
  • G01N2291/0256—Adsorption, desorption, surface mass change, e.g. on biosensors

Definitions

• an adsorption layer and an electrode for adsorbing a sensing object are provided, a sensing sensor using a piezoelectric vibrator whose natural frequency is changed by adsorption of the sensing object, and the sensing sensor is connected to sense.
• the present invention relates to a concentration measuring device for measuring the concentration of a substance in a fluid based on an oscillation output from a sensor.
• a crystal piece is provided as a piezoelectric piece to quantify the mass and concentration of a sensing object contained in a minute amount in the environment or living body, such as a pathological substance such as a prion that causes
• a sensing device using a quartz sensor which is a sensing sensor provided with a quartz vibrator provided with excitation electrodes for exciting quartz pieces on the other side.
• sensing objects include certain proteins in the blood, antibody substances, viruses, and bacteria.
• This type of sensing device includes a quartz sensor, an oscillation circuit, a frequency detection unit that detects the oscillation output of the oscillation circuit, and a display unit that displays the density of the sensing object. It is composed of a measuring instrument and force.
• an adsorption layer in which, for example, an antibody is attached to the surface is provided on one side of the crystal unit, and this antibody selectively adsorbs one of the sensing objects as described above by an antigen antibody reaction. It is like that. Therefore, when the sensing object is adsorbed to the adsorption layer, the frequency of the crystal piece changes according to the amount of adsorption of the sensing object, and the concentration of the sensing object is obtained by using, for example, a calibration curve by obtaining this change. be able to.
• Such sensing devices are described in Patent Document 1 and Patent Document 2, and can measure at the ppt level even for substances that have a large impact on the environment, such as dioxin.
• the resonance frequency of the quartz crystal unit reduces the thickness of the quartz piece.
• the measurement sensitivity of the quartz sensor increases as the quartz piece becomes thinner, so it is possible to measure a very small amount of material by making the quartz piece thinner. Therefore, it is not a large scale like gas chromatography, but it is a simple device and can be analyzed in a short time.
• the type of antibody that is the adsorption layer used in the quartz sensor differs for each sensing object, it must be applicable to the object to be measured, depending on the target object. If a wrong crystal sensor is used by mistake, it will cause a major problem such as the judgment being reversed. However, there is a concern that the crystal sensor may be used incorrectly when measuring many types of sensing objects continuously. In addition, since it is impossible to determine whether or not a sensor is used by appearance, if a malicious case is assumed, there is a concern that a vendor may acquire a used sensor and sell it to the user. If a used adsorption layer is used, the measurement accuracy may be low, or an incorrect measurement result may be generated, resulting in an unexpected situation.
• the user can use the purchased quartz sensor at the start of use or afterwards.
• I want to know information about the quality but I have to read the packaging container and instructions, and record it again.
• managing each crystal sensor in pairs with packaging containers is cumbersome, for example, when there are a large number of specimens or types of objects to be detected, or when measuring outdoors. There is also.
• the packaging container is often discarded.
• Patent Document 2
• the present invention has been made under such circumstances.
• the purpose of the present invention is to provide a user with simple information such as information on quality when measuring a sensing target substance in a fluid using a sensing sensor.
• Another object of the present invention is to provide a convenient sensor that can be accurately and accurately known, and a concentration meter connected to the sensor.
• the sensing sensor of the present invention is provided with an adsorption layer and an electrode for adsorbing a sensing object, and a piezoelectric vibrator whose natural frequency is changed by the adsorption of the sensing object, and an electrode electrically connected to the electrode of the piezoelectric vibrator.
• the detection sensor includes a liquid storage unit to which a sample solution containing a detection target is supplied.
• the information storage unit includes, for example, a memory provided in an integrated circuit element, and the information storage unit includes a bar code read by an optical reading unit on the measuring instrument side or a data storage unit.
• the unique information is information for assuring quality, for example, specifically, Manufacturer, serial number, date of manufacture and quality assurance period.
• the unique information may be a sensing object sensed by the sensing sensor, and in this case, it is preferable to include a concentration standard value of the sensing object. Further, the unique information may be information indicating whether or not the sensing sensor has been used, or may be the type of the adsorption layer.
• the sensing device of the present invention includes a sensing sensor of the present invention, an oscillation circuit for detachably connecting the sensing sensor via a terminal portion, an oscillation circuit for oscillating the piezoelectric vibrator, and an oscillation output from the oscillation circuit
• a measurement unit for measuring the concentration of the sensing object in the fluid a concentration measuring device comprising: means for decoding information in the information data storage unit of the detection sensor; and processing the decoded information And an information processing unit.
• the sensing device includes a display unit that displays decoded information, for example.
• the concentration measuring device may include a means for writing used information in an information data storage unit of the sensing sensor after using the sensing sensor.
• the information processing unit may include a means for determining whether the sensor is a used sensor based on the decoded information and notifying that the sensor has been used.
• the present invention uses a piezoelectric vibrator such as a crystal vibrator and is a sensor that is detachably connected to a concentration measuring device, and stores information unique to the sensing sensor that is decoded by the concentration measuring device. Since the specific information is read out by the concentration meter by connecting the sensor to the concentration meter, it is easy and accurate to identify what the sensor is like. It is convenient to know. Specific information can include, for example, information on quality, information on sensing objects, or information on whether or not the sensing sensor has been used. Can be prevented. Brief Description of Drawings
• FIG. 1 is an overall configuration diagram of a sensing device in which a crystal sensor and a concentration measuring device according to an embodiment of the present invention are combined.
• Fig. 2 shows an example of a crystal sensor and a measuring instrument main body constituting the sensing device.
• Figure 3 is a vertical side view of the quartz sensor.
• FIG. 4 is a plan view showing a printed circuit board of the crystal sensor.
• FIG. 5 is an explanatory diagram showing a crystal resonator and peripheral wiring constituting the crystal sensor.
• Figure 6 is a flowchart showing the procedure for using the sensing device.
• FIG. 7 is an explanatory diagram illustrating an example of a screen displayed on the display unit of the sensing device.
• FIG. 8 is a flowchart showing a procedure when using the sensing device in another embodiment of the present invention.
• FIG. 9 is a flowchart showing a procedure when the sensing device is used in another embodiment of the present invention.
• FIG. 1 is an overall configuration diagram of an embodiment of a sensing device including a concentration meter in a fluid and a sensing sensor according to the present invention.
• the portion surrounded by the chain line 10 in FIG. 1 is a quartz sensor that is a sensing sensor, and includes a quartz crystal (piezoelectric transducer) 1 1 having a crystal piece as a piezoelectric piece and an IC chip 5 that is an integrated circuit element.
• reference numeral 21 denotes a terminal portion on the measuring instrument side to which the electrode of the crystal resonator 11 is connected.
• 5 1 and 5 2 are a signal line terminal and a power line terminal on the measuring instrument side connected to the I C chip 5 respectively. The signal line and the power line are displayed in one line for simplicity.
• the crystal resonator 11 is connected to the oscillation circuit 22 through the terminal portion 21.
• An AZD (analog / digital) converter 23 is provided in the subsequent stage of the oscillation circuit 22, and a frequency detector 24 is provided in the subsequent stage of the A / D converter 23. This frequency detector 24 is connected to the bus 31.
• Each part after the oscillation circuit 22 is a measuring device (concentration measuring device of the present invention) 20.
• 3 2 is a CPU (central processing unit) which is a calculation unit
• 3 3 is a measurement program.
• This measurement program 33 is used to detect the difference in the oscillation frequency of the quartz crystal 11 when the solvent is placed in the quartz sensor 10 and when the sample solution is placed. Steps such as a wave number difference detection step and a calculation of the concentration value of the sensing object calculated from the frequency difference can be executed.
• 34 is a work memory, and is an area for performing calculations for obtaining the concentration of the sensing object in the sample solution from the frequency detected by the frequency detector 24.
• 35 is a sensor data processing program that reads and processes data (sensor data) in a memory provided in the IC chip 5 of the crystal sensor 10.
• 36 is a sensor data memory composed of, for example, a nonvolatile memory, and is a part for storing the sensor data.
• Reference numeral 8 denotes a display unit, for example, a monitor.
• 37 is an operation unit, which is composed of, for example, a keyboard, a mouse, and a screen displayed on the display unit.
• 39 is a serial Z parallel conversion unit that converts serial data from the I C chip 5 into parallel data
• 39 a is a power supply unit that supplies voltage to the I C chip 5.
• FIG. 2 shows an example of a specific structure of each part constituting the sensing device of FIG.
• reference numeral 41 denotes a measuring instrument main body that forms part of the concentration measuring instrument, and includes the oscillation circuit 22, the AZD converter 23, and the frequency detector 24 described in FIG. 1.
• Eight insertion ports 40 are provided on the front surface of the measuring instrument main body 41, and a maximum of eight crystal sensors 10 are removably attached to these insertion ports 40, respectively. .
• a terminal portion 21 shown in FIG. 1 is provided in the insertion port 40.
• a terminal on the side of the crystal sensor 10 described later is provided.
• Printed wiring corresponding to the part 14 a, 14 b and the terminal part 21 provided in the insertion port 40, and the signal of the IC chip 5 on the crystal resonator 10 side The printed wiring 5 3 corresponding to the terminal portion of the line and the printed wiring 5 4 corresponding to the terminal portion of the power supply line are connected, respectively.
• the measuring instrument body 41 and the crystal sensor 10 are electrically connected.
• This sensing device has an 8-channel configuration, and as described above, the quartz crystal sensor 10 is electrically connected to the measuring instrument body 41.
• the oscillation circuit 22 in FIG. The output of each channel is switched and output to the frequency detection unit 24 via the A / D conversion unit 23.
• the quartz sensor 10 has a rubber sheet 4 3 stacked on a wiring board, for example, a printed circuit board 4 2, and closes the recesses 4 4 provided on the rubber sheet 4 3.
• a crystal resonator 11 is provided, and an upper lid case 4 5 is mounted from above the rubber sheet 4 3.
• an inlet 46 for injecting a sample solution as a fluid to be measured and an observation port 47 for the sample solution are formed.
• the sample solution is injected from the inlet 46, and crystal vibration
• the space on the upper surface side of the child i 1 is filled with the sample solution (the crystal piece is immersed in the sample solution).
• the part filled with the sample solution in the quartz sensor 10 corresponds to the liquid container.
• the lower surface side of the quartz resonator 11 is made into an airtight space by the concave portion 44, thereby forming a Langevin type quartz sensor. .
• An IC chip 5 is mounted on the printed circuit board 42, and an arrangement space for the IC chip 5 is formed by forming a through hole in the rubber sheet 43 and covering the upper part with an upper cover case 45. ing. Furthermore, as shown in FIG. 4, the printed circuit board 42 is formed with a printed wiring 53 that is a signal line and a terminal portion of the IC chip 5, and a printed wiring 5 that is a power supply line and a terminal portion of the IC chip 5. 4 is formed.
• the crystal unit 11 has, for example, electrodes 1 3 a and 1 3 b ( The back surface side electrode 13 b is continuously formed on the peripheral portion of the front surface side).
• Electrodes 13 a and 13 b are electrically connected to printed wirings 14 a and 14 b provided on the printed circuit board 4 2 through conductive adhesives 49, respectively.
• an adsorption layer (not shown) made of an antibody that captures a sensing object by an antigen-antibody reaction is formed on one surface side of the crystal resonator 11, for example, the surface of the circular portion of the electrode 13 a, for example. ing.
• a computer such as a personal computer is connected to the measuring instrument main body 41, and the measuring instrument main body 41 and a personal computer constitute a concentration measuring instrument.
• Figure :! 2 corresponds to the oscillation circuit 2 2, the analog / digital converter 2 3, the frequency detector 2 4, and the power source 3 9 a in the measuring instrument body 4 1, the bus 3 1 and this The part connected to the bus 31 is provided on the personal computer side.
• the memory provided in IC chip 5 is a crystal sensor 10 corresponds to an information storage unit that stores unique information.
• This unique information is, for example, information for guaranteeing the quality of the quartz sensor 10.
• it is a manufacturer of the quartz sensor 1 °. .
• the serial number, the manufacturing date and the quality assurance period of the quartz sensor 10 which are unique information are also stored in the memory.
• the quality assurance period includes the date of quality assurance expiration.
• Sensing object to be sensed concentration standard value of the sensing object and information corresponding to the type of quartz crystal 1 1 are included. In this embodiment, these data are also stored in the memory. .
• the sensing object is a substance that the adsorption layer provided on the quartz sensor 10 captures by antigen-antibody reaction, such as dioxin, PCB, prion, etc., but some other proteins, antibody substances, viruses, Examples include bacteria.
• the concentration standard value can include, for example, an allowable concentration such as the concentration of contaminants in water, and the allowable concentration is not limited to the value stipulated by laws and regulations. It may be.
• the sensor data processing program 35 provided in the concentration measuring device 20 (provided in the personal computer in this example) will be described.
• This program 35 is stored in the memory provided in the IC chip 5. Steps for reading data and writing to sensor data memory 36, steps for displaying the data and data processing results on display unit 38, crystal sensor with quality guaranteed based on these data 1
• a step of determining whether or not the value is 0, for example, a step of determining whether or not the manufacturer is a predetermined manufacturer and whether or not it is within the quality assurance period is included.
• the use of a replica of the crystal sensor 10 is prevented by having a step for determining whether or not it is within the quality assurance period.
• the program 35 corresponds to a means for decoding data in the memory provided in the IC chip 5 (decoding unit) and a means for processing data. You can also encrypt the data in IC chip 5.
• the program 35 further includes a step of determining whether or not the measurement target substance input by the operator is a detection target assigned to the quartz sensor 10, and when the concentration of the detection target can be measured, The measured value is compared with the standard concentration value. Includes a step of determining whether or not is within a standard value. Furthermore, the program 35 includes a step for performing processing such as display of determination results and output of warning in each step, for example, display on a screen and output of alarm sound.
• the measuring instrument body 41 may be provided with a liquid crystal display.
• FIG. 6 is a flowchart for explaining the operation.
• the quartz sensor 10 is inserted into the insertion port 40 of the measuring instrument main body 41 and attached (Step S 1).
• the quartz crystal resonator 11 and the IC chip 5 of the quartz sensor 10 are connected to the concentration measuring device 20 as described above.
• the concentration measuring device 20 as described above.
• Concentration measuring instrument 20 IC sensor program 3 5 IC chip
• the sensor data stored in the memory 5 is read out and displayed on the display unit 38 (step S 2).
• FIG. 7 shows an example of the screen of the display unit 38 displaying this sensor data.
• This screen displays the manufacturer, serial number, manufacturing date, quality assurance period, sensing object, concentration standard value, crystal oscillator information, and customer code of the crystal sensor 10.
• the crystal oscillator information is information corresponding to the type of crystal piece used in the crystal sensor 10 and includes, for example, a numerical value of weight change per 1 Hz change. In other words, by knowing this value, it is possible to know the weight change with respect to frequency change (the amount of adsorption of the sensing object).
• the customer code is a code assigned to the user to whom the crystal sensor 10 is delivered.
• the operator confirms these display contents (step S3). For example, look at the quality assurance period, determine whether the quartz sensor 10 is within the quality assurance period, and confirm whether the sensing object matches the object to be measured.
• a predetermined amount of a solvent for example, pure water
• a predetermined amount of a solvent for example, pure water
• the quartz crystal 1 1 is oscillated by the oscillation circuit 2 2 after being immersed in water.
• the oscillation output of this crystal unit 11 after oscillation has stabilized after a predetermined time has passed is input to the frequency detection unit 24, and the frequency f 1 at which this crystal unit 11 oscillates by this frequency detection unit 24. Is measured (step S 4).
• a sample solution to be examined for the concentration of the substance to be measured for example, a river for measuring the concentration of dioxin
• a sample solution to be examined for the concentration of the substance to be measured for example, a river for measuring the concentration of dioxin
• the crystal resonator 11 is immersed in the sample solution.
• the frequency f 2 at which the crystal resonator 11 oscillates is measured by the frequency detector 24 (step S 5).
• the method for obtaining the frequency f 2 is not limited to this example.
• pure water is injected into the crystal sensor 10, the pure water is discarded from the crystal sensor 10, and then the sample solution is supplied to the crystal sensor 10. And set the oscillation output to a stable value of ⁇ 2.
• the measured frequencies f 1 and f 2 are written to the work memory 3 4 respectively, and the frequency difference (f 1-f 2) between f 1 and f 2 is calculated by the measurement program 3 3 in this single memory 3 4.
• step S 6 by creating a calibration curve for each sensing object in advance and storing it in a separate memory, and providing a program for calculating the concentration of the sensing object based on the calibration curve, (f 2 When fl — is obtained, the concentration of the sensing object is obtained (step S 6).
• the concentration of the sensing object such as dioxin in the sample solution thus obtained is displayed on the display unit 38 together with the value of the frequency difference (f 2 ⁇ fl) (step S 7).
• the operator can determine whether or not the concentration is lower than the allowable concentration by comparing with, for example, the standard value of dioxin (in this case, the allowable concentration) read from the quartz sensor 10. This determination may be automatically performed using the steps incorporated in the program and displayed together.
• the information displayed on the display unit 38, that is, the information unique to the crystal sensor 10 and the measurement result are stored in the memory in association with each other (step S8) so that they can be retrieved later.
• the quartz sensor 10 is attached to the concentration measuring device 20.
• the unique information is read from the IC chip 5 of the crystal sensor 10, so that it is easy to know exactly what the crystal sensor is like, which is convenient.
• the information is related to quality, such as the manufacturer and quality assurance deadline, the user can check the quality, and the management of the adsorption layer provided in the quartz sensor 10 is controlled by the measurement accuracy.
• quality can be assured of accurate measurement. Since the data in the IC chip 5 is difficult to read, it is possible to prevent the pirated version from circulating, and it is guaranteed that the user can use the genuine product, and the user can be protected. From this point, it is preferable to encrypt the data.
• the sensing object of the quartz sensor 10 in the IC chip 5 as unique information, it is possible to prevent mistakes in the quartz sensor 10 and to include the standard value of the sensing object. Convenient for measurement. Furthermore, if such unique information is extracted from the quartz sensor 10 and stored in the concentration measuring instrument 20 in association with the measurement result, there may be a problem in the quality of the quartz sensor 10, for example. Even if it is, it is convenient to contact the manufacturer when analyzing and examining the measurement results later.
• This embodiment has a read / write function for the memory in the IC memory 5 of the crystal sensor 10 (nonvolatile memory in this example), and the terminal 51 has read / write control. A signal path is also included.
• the sensor data processing program 35 for example, at the time when the measurement of the frequency f2 of the crystal sensor 10 is completed after the crystal sensor 10 is used, And whether or not the crystal sensor 10 has been used based on information read from the memory in the IC memory 5 of the crystal sensor 10 And a program for displaying the fact on the display unit 3 8 if it has been used.
• the second embodiment has the same configuration as that of the first embodiment except for these portions. The operation of this embodiment will be described with reference to FIGS.
• the quartz sensor 10 is inserted into the insertion port 40 of the measuring instrument main body 41 and attached.
• the instrument body 41 is turned on, and the following series of processing is performed by the sensor data processing program 35 of the concentration measuring instrument 20.
• the used / unused determination information is read from the sensor data stored in the memory of the IC chip 5 (step 11), and it is determined whether or not the crystal sensor 10 has been used (step 12). . If it is determined that it has been used, a warning is displayed on the display unit 3 8 indicating that it has been used (step 13). If it is determined that it has not been used, it is stored in the memory of the IC chip 5.
• the expiration date information (quality assurance date) is read from the sensor data stored (step 14), and it is determined whether or not the crystal sensor 10 is within the expiration date range (step 15). If it is determined that the time limit has been exceeded, a warning message indicating that the time limit has been exceeded is displayed on the display unit 3 8 (step 16). If it is determined that the time limit has been exceeded, a sensor is displayed on the display unit 38. Data, for example, as shown in Fig. 7, the manufacturing force, manufacturing number, manufacturing date, quality assurance period, sensing target, concentration standard value, crystal oscillator information, customer code, etc. of the quartz sensor are displayed. Step 1 7).
• the type of the antibody which is the aforementioned adsorption layer provided on the electrode 13 of the crystal sensor 10, is written in the memory of the IC chip 5 as specific information of the crystal sensor 10, and this information is stored in the memory. It is also possible to read it from and display it on the display unit 38.
• the operator measures the frequency of the sensing target part (step 18).
• the frequency measurement is performed by the same operation as Step 4 to Step 6 of the first embodiment described above (Step 19), and the measurement result of the sensing object in the sample solution thus obtained is displayed on the display unit 38. (Step 20).
• the used data is written in the memory of the IC chip 5 (step 22), and a warning is displayed on the display unit 38 (step 23). .
• frequency measurement is performed using an unused crystal sensor 10, and then automatically used in the sensor data stored in the memory provided in the IC chip 5.
• Already used data and when using a crystal sensor, it is determined whether or not the crystal sensor has been used, so there is a risk of frequency measurement using the used crystal sensor by mistake. It is possible to protect users and avoid unexpected situations.
• the present invention is not limited to measuring a substance in a liquid as a substance in a fluid, but can also be applied to measuring a toxic substance such as sarin gas or hydrogen sulfide gas in a gas.
• the information storage unit is not limited to the IC chip but may be a barcode.
• an optical reader that reads the barcode is provided at the insertion port 40 on the measuring instrument body 41 side, and the insertion port on the measuring instrument body 41 side on the printed circuit board 42 of the crystal sensor 10
• a bar code displaying unique information may be provided at a position corresponding to the optical reader when inserted into 40.
• the information storage unit may be magnetic data such as that used in a bank cash card.
• magnetic data is formed on the surface of the printed circuit board 42 of the quartz sensor 10 and the measuring instrument body 41 side. This magnetic data is configured to be read by the measuring instrument main body 41 when it is inserted into the insertion port 40.

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• 2006
  • 2006-07-31 JP JP2006209207A patent/JP4439500B2/ja not_active Expired - Fee Related
  • 2006-12-12 US US12/159,233 patent/US8352198B2/en not_active Expired - Fee Related
  • 2006-12-27 CN CN200680049841.5A patent/CN101351695B/zh not_active Expired - Fee Related
  • 2006-12-27 EP EP06843751A patent/EP1967838A1/en not_active Withdrawn
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